Process for the treatment of keratinous fiber and resulting article



Patented May 11, 1954 PROCESS FOR THE TREATMENT OF KERATINOUS FIBER AND RESULTING ARTICLE Walter M. Bruner and James C. Lehr, Wilmington, Del., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application August 24, 1949, Serial No. 112,178

6 Claims. (01. 117- 141) l This invention relates to a method for the treatment of keratinous textile fibers and especially wool in the form of woolen fabric or, garments and the like, whereby it may be ren-' 'dered'subs'tanti'ally non-shrinkable without any appreciable or detrimental alteration of its desirable characteristics.

'Keratinous fibers tend to shrink and/or felt during washing thereby destroying to a large extent their commercial value. In the description of this invention the term felt is to be understood to refer'to thatproperty of such fibers which causes them to close upon each other in washing, or other treatment in aqueous liquor in which the wool material is repeatedly squeezed and rubbed, so that the keratinous material becomes denser and more compact. This property of felting is primarily, responsible for shrinkage prove the physical characteristics of wool. Another object is the treatment of wool and similar keratine-ccntaining fibers to reduce their tenlaundering. A further object is the reduction in the tendency of woolto shrink on laundering. Yet another object is the provision of wool-containing fibers of reduced tendency to shrink on laundering, which fibers retain their natural water repellency, resiliency when wet, and softness. Other objects and advantages of the invention will hereinafter appear.

According to the present invention, the tendency of keratinous fibers as raw filaments, yarn, knit, woven goods or mixed good to felt and shrink on laundering in aqueous liquors is reduced by treating the fibers with a high molecular weight substituted hydrocarbon polymer or like addition agent and a fixative. This treatment is carried out by bringing the addition agent and fixative together in the fibers and subjecting the mixture to a curing operation which firmly holds the addition agent and fixative on the fibers. As a result of this treatment the felting and shrinking of the wool is remarkably inhibited, it being possible to decrease these undesirable properties from a normal of 50% to 5% or less. Moreover, materials containing wool which have already been partially felted may have their further feltingtendencies inhibited by the process herein described. It is believed, although this does not limit the .dency to felt on mechanical working and during invention, that the action of the addition agent and the fixative is mainly confined to the surface of the fiber and that any substantial extension of this action to the interior of the fiber does not occur. The term "quali is understood to refer to the properties of wool such as tensile strength, softness of handle, color and durability which have to be taken into account in assessing the value and usefulness of wool material. In general the quality is reduced if the wool suffers the loss of weight and is made weaker, harsher, yellower and less durable.

The material treated by the process of the invention retains its improved quality and resistance to shrinking even after repeated washing. The addition agent appears to be the principal substance applied that inhibits the shrinking, felting and like undesirable properties of wool and like materials. These agents should be present to the extent of from not less than about 1% to not more than about 25% based on the weight of the keratinous material. The fixative which appears to act as a cross-linking agent between the molecules of the addition agent and possibly the wool should be present to the extent of from 0.01% to.10% based on the weight of the impregnant solution.

The treatment with the high molecular weight substituted hydrocarbon and the fixative may conveniently be carried out as follows: The substituted high molecular weight hydrocarbon, polymer or other addition agent and a suitable solvent therefor are tumbled at room-temperature to give a solution of polymer concentration in the range of l to 20%, preferably 1 to 5% of the addition agent. To 150 parts of the resulting solution there is added 0.005 to 0.5% of a fixative. A standard wool swatch 7" x '7" is immersed in the solution for 5 minutes. The swatch is then run through a set of rubber or metal squeeze rolls five times, rewetting the swatch in the solution after each of the first four times. The swatch,

curing it to a wooden frame without stretching and placing in a circulating air oven at the desired temperature for the desired period of time. The cured swatch is washed by placing in a receptacle with 15 solid rubber balls, about inch in diameter and parts of soap solution containing about 0.2% by weight of soap flakes and 0.1% byweight of sodium carbonate .to 5%. be present about 2% of the agent and preferably between 4 and 5% as indicated in Examples 11, 6 and '7 respectively. In Example 5 in distilled water. The temperature at the start of washing is 50 C. The receptacle and contents are placed on a large Red Devil Paint Mixer and shaken for 15 minutes. The swatch is rinsed with warm water, measured wet and recharged to the container along with a fresh batch of soap solution for a second 15 minute 4 ing influence is clear from the other examples showing the use of a fixative.

The addition agents used, generally high molecular weight substituted hydrocarbons, to produce the decrease in felting and shrinking include the halogenated as well as the halogenated and sulphonated high molecular weight wash. The swatch is again rinsed, measured, air dried and re-measured. The percent area of shrinkage is equal to 100 minus the percent re-measured area over the original area.

Table I illustrates the effectiveness of a number of addition agents which inhibit the shrinking of wool when the wool is treated with the agent in the presence of the fixative described. The agents of Table I, containing both chlorine and sulfur dioxide, were chlorosulfonated in accord with the process described in the later I mentioned Patent 2,212,786, while the agents which have been only chlorinated were chlorinated in-accord with "the. technique described .in the-McAlevy Patent 2,405,971.

. Table I Substitution Fixative Curing Ilkliluene Agent 812N311 k ufion, on r Agent Used Per- Per- Per- Time Tem Percent D ispersion Wool, age,

cent cent Kind cent Min 0 X Percent Percent 1. Polyisobutylene Vistanex B-40 27. 7 3. 75 N 0.1 150 10 10 2. Polyisobutylene Vistanex B-40 27. 7 3. 75 N 0. 1 5 150 5 5 36 3. Hydrogenated Rubber (smoked sheet), 27 1. 39 M 0.075 5 150 5 5 9 4. Hydrogenated Rubber (smoked sheet). 27 1. 39 M 0.02 5 150 2 2 5 5. Pclymerofethylcne (1\l,Wl8,000-19,G0 27.8 2.0 5 150 5 5 37 6. Polymer-Methylene (MW 18,000l9,000) 27.7 1.5 2 150 4 4 8 7. Polymeroicthylene(MW18,00019,000). 27.7 1.5 2 150 5 5 9 8. Polymeroiethylene (MW 18,000494100). 27.7 1.5 2 150 7 7% 5 9. Polymcrofethylcne (lVlW18,000-10,000). 28.4 3.8 M 0. 02 5 150 2 2 12 10. Polgymg; of ethylene (MW 18,000- 26 4.5 M- 0.05 3 150 5 5 5 l 00 ll Polyme; of ethylene (WW 18,000- 26 4.5 M 0.01 5 2 6 19 000 v I I 12 Pogyglicg of ethylene (MW 18,000 27.7 1 5 N 0.1 10 6.8 4 14 1 0 7 13 Polginne; of ethylene (MW 18,000- 27.7 15 N 0.1 5 9.6 10

l 000 14 Polyme; of ethylene (MW 10,000- 5 2 2 M 0.075 5 5 12 11 000 l5 Polyme)r of ethylene (MW 10,000- 29.3 6 4 M 0.02 5 150 3 3 9 11 000 10 Prlflgymer of ethylene (MW 18,000- 32.9 0 M 0.2 5 150 5 5 10 .00 17. Neoprene M 0.2 5 150 5 5 4 18. Neoprene. M 0.05 5 150 2 2 7 19. Neoprene 5 150 2 2 39 20. Chlorinated rubber... M 0.2 5 150 10 '10 5 N=Hexamethylenediamine.'

M=3-Methoxyhexamethylenediamine. X=B y weight of solution.

while with hydrogenated rubber, Examples 3 and 4, 2% gives a shrinkage of 5% which is not improved by increasing the percent of the agent With ethylene polymers there should is shown the efiectiveness of a chlorosulfonated polymer of ethylene alone and Example 20 the effectiveness of neoprene alone. While unaided such polymers inhibit shrinking, the ,utilityof a fixative to improve their inhibitare first either chlorinated or chlorinated and then treated with sulfur dioxide to give chlo= rinated or chlorosulfonated hydrocarbons. The chlorosulfonation process described in the McQueen Patent 2,212,786 may be employed or any other suitable process while the chlorinated hydrocarbons may be produced in accord with the process described for the halogenation of ethylene polymers in the McAlevy patent supra".

The fixatives employed are poly-functional organic compounds and may contain polyhydroxy, polymer-capto, polyamino or polyamide groups. Specific fixatives which may be used include the polyhydric alcohols such, for example, as ethylene glycol, propylene glycol, diethylene glycol, hexamethylene glycol, octadecandiol andthe like; the poly-functional mercaptan containing compounds such, for example, as ethane dithiol, propane dithiol and the like; the polyamino compounds such, for example, as ethylene diamine, propylene diamine, hexamethylene diamine, hexamethylenetetramine, N -isobutyl hexamethylene diamine, N-Nediisobutylhexamethylene;di-

amine, and the like; the carbamates such, for example, as methoxymethoxyethyl, carbamate, hydroxypropyl carbamate, N-N'-dialkyl ureas such as N-N'-diisobutyl urea and the like; the diamides such, for example, as those obtained by the reaction of dicarboxylic acids such, for example, as adipic, suberic acids, etc, with diamines such as hexamethylene diamine and related diamines. Unsymmetrical poly-functional compounds may likewise be employed such as ethanolamines, ethanol mercaptans, ethanol amides and the like.

While the curing of the wool with the high molecular weight substituted hydrocarbon polymer and other addition agent and the fixative is conducted in the examples at a temperature of 150 C. this temperature is not critical for temperatures ranging between '75 and 250 C. may be employed if desired. At the higher temperatures a much shorter curing time should be employed and at the lower temperatures a longer curing time to efiect the same degree of shrinkage and felting inhibitions.

In Examples 1 to 11 of the'table and 14 to 20 the treatment was effected by means of a solution of the addition agent and fixative. This solution may be any sulitable organic solvent for the addition agent which likewise is a solvent for the fixative. Inasmuch as the fixative is employed in only very small percentages it is necessary only that the solvent be effected to that extent. Such solvents as toluene, carbon tetrachloride, benzene, chlorinated aromatic hydrocarbons and tetrachloroethylene as well as other suitable solvents may be used if desired.

Examples 12 and 13 illustrate another method of applying the addition agent and the fixative to the wool, these examples describing the use of aqueous dispersions of chlorosulionated ethylene polymer. Any suitable method for preparing dispersions of these and the other treating agents may be employed. The dispersions illustrated were made in this manner: 7

The chlorosulionated polymer of ethylene, to the extent of 20.2% by weight, 9.9% of Tween-20 (fatty acid ester of a polyoxyethylene-sorbitol condensation product) and of medium viscosity sodium carboxymethyl cellulose, the latter two being based on the weight of the chlor sulfonated hydrocarbon, were processed in a dispersing mill. To 18.6 parts of the dispersion was added 56.4 parts of distilled water and 0075 part of hexamethylene diamine. A' wool swatch, 7 x '7", was impregnated in this bath in the manner described above and the swatch cured as indicated.

Any keratinous containing animal fiber, e. g. wool, alpaca, vicuiia, Angora rabbit hair, goat hair, camel hair and the like may be reduced in shrinking tendency by the process of this invention. The material which is to be processed may be in the raw fibrous form or may be in any form, for example, as yarn, thread, knit, woven or mixed goods.

We claim:

1. A process for the treatment of a keratinous fiber which comprises shrinkproofing a keratinous fiber by impregnating it with a solution containing 1 to 20% by weight of a chlorinated high molecular weight polymer of ethylene and 0.005 to 0.5% of a fixative of the class consisting of organic compounds containing polyhydroxy, polymericapto, polyamino and polyamide groups, and thereafter heating the thus impregnated fiber at a temperature between '75 and 250 C.

2. The process of claim 1 in which the keratinous fiber is wool.

3. A keratinous fiber resistant to shrinking and containing from 2 to 10% by weight of a chlorinated polymer of ethylene combined with a fixative of the class consisting of organic compounds containing polyhydroxy, polymercapto, polyamino and polyamide groups.

4. The product of claim 3 in which the keratinous fiber is wool.

5. A keratinous textile fiber resistant to shrinking containing 2 to 10% by weight of a chlorinated polymer of ethylene combined with hexamethylene diamine.

6. A wool fiber resistant to shrinking containing 2 to 10% by weight of a chlorinated polymer of ethylene combined with hexamethylene diamine.

References Cited in the file Of this patent UNITED STATES PATENTS Number Name Date 1,980,959 Schultze NOV. 13, 1934 2,300,920 Heuer Nov. 3, 1942 2,413,163 Bacon Dec. 24, 1946 2,471,456 Rust May 31, 1949 2,503,252 Ernsberger Apr. 11, 1950 2,507,699 Edgar et a1. May 16, 1950 FOREIGN PATENTS Number Country Date 611,828 Great Britain Nov. 4, 1948 

1. A PROCESS FOR THE TREATMENT OF A KERATINOUS FIBER WHICH COMPRISES SHRINKPROOFING A KERATINOUS FIBER BY IMPREGNATING IT WITH A SOLUTION CONTAINING 1 TO 20% BY WEIGHT OF A CHLORINATED HIGH MOLECULAR WEIGHT POLYMER OF ETHYLENE AND 0.005 TO 0.5% OF A FIXATIVE OF THE CLASS CONSISTING OF ORGANIC COMPOUNDS CONTAINING POLYHYDROXY, POLYMERCAPTO, POLYAMINO AND POLYAMIDE GROUPS, AND THEREAFTER HEATING THE THUS IMPREGNATED FIBER AT A TEMPERATURE BETWEEN 75 AND 250* C. 